Process for the preparation of a redispersible dispersion powder composition

ABSTRACT

The invention concerns a dispersion powder composition which is redispersible in water and is made from water-insoluble organic polymers, the composition being characterized in that it contains 0.1 to 30% by wt., relative to the weight of the organic polymers, of one ormore silicon compounds which are dispersible in water and which have a boiling point at normal pressure of 160° C., selected from the group comprising the silanes, polysilanes, oligosiloxanes, carbosilanes, polycarbosilanes, carbosiloxanes, polycarbosiloxanes and polysilylenedisiloxanes. The invention also concerns methods for manufacturing such compositions and their use.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a dispersion powder composition which isredispersible in water and is based on water-insoluble polymers, processfor its preparation and its use.

2. Background Art

Dispersion powder compositions which are redispersible in water and arebased on homo- or copolymers are known. Such a dispersion powdercomposition is prepared by spray drying the corresponding aqueousplastics dispersions in a stream of hot air. The dispersion powders aresuitable as additives to hydraulic binders in the building materialsindustry, and such products are furthermore employed as binders incoating compositions or in adhesives.

EP-A 228657 (U.S. Pat. No. 4,704,416) describes dispersion powders whichare redispersible in water and are based on water-soluble polymers, andwhich comprise organic silicon compounds, preferablyorganopolysiloxanes. The dispersion powders are prepared by spray dryingan emulsion of the organic silicon compound in an agueous solution ofthe water-soluble polymer.

EP-B 279373 relates to powders which are redispersible in water andcomprise organopolysiloxane, and which additionally comprise awater-soluble, film-forming polymer. They are prepared by spray dryingthe acueous mixtures of the constituents mentioned.

EP-A 493168 relates to dispersion powders which are redispersible inwater and are based on film-forming, waterinsoluble vinyl or acrylicpolymers, and which comprise silicones, more precisely organosiliconatesand/or organopolys-loxanes. They are prepared by sprav drying aqueousdispersions of the vinyl or acrylic polymers, to which silicones havebeen added before the spraying.

SUMMARY OF THE INVENTION

The invention is based on the object of providing dispersion powdercompositions which are redispersible in water and are based onwater-insoluble polymers, and which are modified with organosiliconcompounds.

The invention relates to a dispersion powder composition which isredispersible in water and is based on water-insoluble organopolymers,wherein the powder composition comprises 0.1 to 30% by weight, based onthe organopolymer content, of one or more water-dispersible siliconcompounds having a boiling point under normal pressure of >160° C., fromthe group consisting of silanes, polysilanes, oligosiloxanes,carbosilanes, polycarbosilanes, carbosiloxanes, polycarbosiloxanes andpolysilylenedisiloxanes.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Suitable water-insoluble organopolymers are: homo- and copolymers whichare in the form of an aqueous dispersion or which can be converted intoan aqueous dispersion, and which, if appropriate at elevated temperatureand/or in an alkaline medium, form a solid film after drying on and, ifappropriate, hardening. The average particle size of the dispersionpowder particles is in general 1 to 1000 μm, preferably 10 to 700 μm,particularly preferably 50 to 500 μm.

Preferred water-insoluble polymers are: vinyl ester homo- or copolymerscontaining one or more monomer units from the group consisting of vinylesters of unbranched or branched alkylcarboxylic acids having 1 to 15 Catoms;

(meth)acrylic acid ester homo- or copolymers containing one or moremonomer units from the group consisting of methacrylic acid esters andacrylic acid esters of unbranched or branched alcohols having 1 to 12 Catoms; homo- or copolymers of fumaric and/or maleic acid mono- ordiesters of unbranched or branched alcohols having 1 to 12 C atoms;

homo- or copolymers of dienes, such as butadiene or isoprene, and ofolefins, such as ethene or propene, it being possible for the dienes tobe copolymerized, for example, with styrene, (meth)acrylic acid estersor the esters of fumaric or maleic acid; homo- or copolymers of vinylaromatics, such as styrene, methylstyrene or vinyltoluene;

homo- or copolymers of vinyl-halogen compounds, such as vinyl chloride.

where appropriate, water-insoluble, film-forming polyaddition andpolycondensation polymers, such as polyurethanes, polyesters, polyethers(excluding polyethylene oxide), polyamides, melamine-formaldehyde resinsor phenol-formaldehyde resins, if appropriate also in the form of theiroligomeric precursors, are also suitable.

Preferred vinyl esters are vinyl acetate, vinyl propionate, vinylbutyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate,vinyl pivalate and vinyl esters of α-branched monocarboxylic acidshaving up to 10 C atoms, for example VeoVa9^(R) or VeoVa10^(R). Vinylacetate is particularly preferred.

Preferred methacrylic acid esters or acrylic acid esters are methylacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,propyl acrylate, propyl methacrylate, n-butyl acrylate, t-butylacrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexylacrylate. Methyl acrylate, methyl methacrylate, n-butyl acrylate and2-ethylhexyl acrylate are particularly preferred.

Preferred ester groups of fumaric and maleic acid are the methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, hexyl, ethylhexyl anddodecyl group.

If appropriate, the vinyl ester copolymers can comprise 1.0 to 65% byweight, based on the total weight of the comonomer phase, of α-olefins,such as ethylene or propylene, and/or vinyl aromatics, such as styrene,and/or vinyl halides, such as vinyl chloride, and/or acrylic acid estersor methacrylic acid esters of alcohols having 1 to 10 C atoms, such asmethyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate,t-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate and2-ethylhexyl acrylate and/or ethylenically unsaturated dicarboxylic acidesters or derivatives thereof, such as diusopropyl fumarate, or thedimethyl, methyl t-butyl, di-n-butyl, di-t-butyl and diethyl ester ofmaleic acid or fumaric acid, or maleic anhydride.

If appropriate, the (meth)acrylic acid ester copolymers can comprise 1.0to 65% by weight, based on the total weight of the comonomer phase, ofα-olefins, such as ethylene or propylene, and/or vinyl aromatics, suchas styrene, and/or vinyl halides, such as vinyl chloride and/orethylenically unsaturated dicarboxylic acid esters or derivativesthereof, such as diisopropylfumarate or the dimethyl, methyl t-butyl,dibutyl and diethyl esters of maleic acid or fumaric acid, or maleicanhydride.

In a preferred embodiment, the vinyl ester copolymers and the(meth)acrylic acid ester copolymers also comprise 0.05 to 10.0% byweight, based on the total weight of the comonomer mixture, of auxiliarymonomers from the group consisting of ethylenically unsaturatedcarboxylic acids, preferably acrylic acid or methacrylic acid; from thegroup consisting of ethylenically unsaturated carboxylic acid amides,preferably acrylamide; from the group consisting of ethylenicallyunsaturated sulfonic acids and salts thereof, preferably vinylsulfonicacid; and/or from the group consisting of polyethylenically unsaturatedcomonomers, for example divinyl adipate, diallyl maleate, allylmethacrylate or triallyl cyanurate. Suitable auxiliary monomers are alsocomonomers having a crosslinking action, for example acrylamidoglycolicacid (AGA), methacrylamidoglycolic acid methyl ester (MAGME),N-methylolacrylamide (NMAA), N-methylolmethacrylamide, allylN-methylolcarbamate and alkyl ethers, such as the isobutoxy ether, oresters of N-methylolacrylamide, of N-methylolmethacrylamide or allylN-methylolcarbamate.

Corresponding statements to those for the (meth)acrylic acid estercopolymers apply to the copolymers of esters of maleic or fumaric acid.

The water-insoluble polymers mentioned which can be polymerized by freeradicals are preferably prepared by the emulsion polymerization process.The polymerization can be carried out discontinuously or continuously,with or without the use of seed latices, with initial introduction ofall the constituents or individual constituents of the reaction mixture,or with initial introduction of a portion and subsequent metering of theconstituents or individual constituents of the reaction mixture, or bythe metering method without an initial mixture. All the meterings arepreferably carried out at the rate of consumption of the particularcomponent. The polymerization is preferably carried out in a temperaturerange from 0 to 100° C., and is initiated using the methods usuallyemployed for emulsion polymerization. The initiation is carried out bymeans of the customary, water-soluble agents which form free radicals,which are preferably employed in amounts of 0.01 to 3.0% by weight,based on the total weight of the monomers. All the emulsifiers and/orprotective colloids usually used in emulsion polymerization can beemployed as dispersing agents.

If appropriate, up to 6% by weight, based on the total weight of themonomers, of emulsifier is employed. Possible emulsifiers here are bothanionic and cat-onic as well as nonionic emulsifiers, if these areinsoluble in the protective colloid. Protective colloids are preferablyemployed, particularly preferably in amounts of up to 15% by weight,based on the total weight of the monomers. Examples of these arepolyvinyl alcohols and derivatives thereof; such as vinyl alcohol/vinylacetate copolymers, polyvinylpyrrolidones; polysaccharides inwater-soluble form, such as starches (amylose and amylopectin),cellulose, guar, tragacanthic acid, dextran, alginates andcarboxymethyl, methyl, hydroxyethyl and hydroxypropyl derivativesthereof; proteins, such as casein, soya protein and gelatin; syntheticpolymers, such as poly(meth)acrylic acid, poly(meth)acrylamide,polyvinylsulfonic acids and water-soluble copolymers thereof;melamlne-formaldehydesulfonates, naphthalene-formaldehydesulfonates, andstyrene/maleic acid and vinyl ether/maleic acid copolymers. In the mostpreferred embodiment, the polymerization is carried out with aprotective colloid and without addition of an emulsifier.

Suitable water-dispersible silicon compounds from the group consistingof silanes, polysilanes, oligosiloxanes, carbosilanes, polycarbosilanes,carbosiloxanes, polycarbosiloxanes and polysilylenedisiloxanes are thosewhich have a boiling point under normal pressure above 160° C. Compoundswhich are preferably employed are silanes, such as tetraorganosilanesSiR₄, silicic acid esters Si(OR′)₄, organoorganoxysilanes SiR_(n)(OR′)_(4−n), where n=1 to 3, polysilanes of the general formulaR₃Si(SiR₂)_(n)SiR₃ where n=0 to 500, preferably 0 to 8, andoligosiloxanes of the general formula R₃SiO(SiR₂O)_(n)SiR₃ where n=0 to4, in which R′ represents identical or different alkyl radicals oralkoxyalkylene radicals having 1 to 4 C atoms, and preferably denotesmethyl or ethyl, and R is identical or different and denotes branched orunbranched alkyl radicals having 1 to 22 C atoms, cycloalkyl radicalshaving 3 to 10 C atoms, alkylene radicals having 2 to 4 C atoms, oraryl, aralkyl or alkylaryl radicals having 6 to 18 C atoms, it alsobeing possible for the radicals R mentioned to be substituted byhalogens, such as F or Cl, or by ether, thioether, ester, amide,nitrile, hydroxyl, amine, carboxyl, sulfonic acid, carboxylic acidanhydride and carbonyl groups, and in which, in the case of thepolysilanes and oligosiloxanes, R can also have the meaning OR′.

Particularly preferred silicon compounds are, for example,tetraethoxysilane, methyltripropoxysilane, methyltri (ethoxyethoxy)silane, vinyltri (methoxyethoxy)silane, (meth)macryloxypropyltriethoxy-or -trimethoxysilane, γ-chloropropyltriethoxysilane,β-nitriloethyltriethoxysilane, mercaptopropyltriethoxy- or-trimethoxysilane, phenyltriethoxysilane, iso-octyltriethoxysilane,dipropyldiethoxysilane, methylphenyldiethoxysilane,diphenyldimethoxysilane, methylvinyltri(ethoxyethoxy)silane and di-and/or trisiloxanes thereof. Hexamethyldiethoxytrisiloxane,octamethylcyclotetrasiloxane, tetramethyldiethoxydisilane,trimethyltrimethoxydisilane, dimethyltetramethoxydisilane, orcondensation products thereof, and pentamethyldisilane-disiloxane mayfurthermore be mentioned. The silicon compounds mentioned can beemployed by themselves or as a mixture.

The organosilicon compounds can be prepared by processes such as aredescribed in Noll, Chemie und Technologie der Silicone [Chemistry andtechnology of the silicones], 2nd edition 1968, Weinheim and inHoubenWeyl, Methoden der organischen Chemie [Methods of organicchemistry], Volume E20, page 1782 et seq., 2219 et seq., Georg ThiemeVerlag, Stuttgart, 1987.

The water-dispersible organosilicon compounds are preferably present inan amount of 0.5 to 15% by weight, based on the organopolymer content.

The silicon compounds are preferably added in the form of an emulsion tothe organopolymer dispersion to be sprayed. The protective colloidsbelow, if appropriate in combination with suitable emulsifiers, arepreferably used for the emulsification. Possible emulsifiers here areboth anionic and cationic as well as nonionic emulsifiers. Those whichare not soluble in the protective colloid and have relative molecularweights, in contrast to the protective colloids, of less than 2000 arepreferred. Suitable emulsifiers are known to the expert and are to befound, for example, in Houben-Weyl, Methodem der organischen Chemie[Methods of organic chemistry], Volume XIV, 1, Makromolekulare Stoffe[Macromolecular substances], Georg Thieme Verlag, Stuttgart, 1961,192208. The emulsifiers are as a rule employed in amounts of up to 5% byweight, based on the silicon compounds. The amount is preferably <1% byweight, based on the organopolymers.

In a preferred embodiment, the dispersion powder composition comprises 8to 50% by weight, preferably to 25% by weight, of protective colloid,based on the total amount of water-insoluble organopolymer and siliconcompound. Suitable protective colloids are, for example, polyvinylalcohols and derivatives thereof; polysaccharides in water-soluble form,such as starches (amylose and amylopectin), cellulose, guar,tragacanthic acid, dextran, alginates and carboxymethyl, methyl,hydroxyethyl and hydroxypropyl derivatives thereof; proteins, such ascasein, soya protein and gelatin; synthetic polymers, such aspoly(meth)acrylic acid, poly(meth)acrylamide, polyvinylsulfonic acidsand water-soluble copolymers thereof; melamine-formaldehydesulfonates,naphthalene-formaldehydesulfonates, and styrene/maleic acid and vinylether/maleic acid copolymers.

Further constituents of the dispersion powder composition whichpreferred embodiments comprise are antiblocking agents, such as Cacarbonate or Mg carbonate, talc, gypsum, silicic acid and silicateshaving particle sizes preferably in the range from 10 nm to 10 μm.

The dispersion powder composition is prepared by means of spray drying.Drying is carried out here in the customary spray drying units, it beingpossible for the atomization to be effected by means of one-, two- ormulti-comoonent nozzles or with a rotating disc. The dischargetemperature is in general chosen in the range from 55° C. to 100° C.,preferably 70° C. to 90° C., depending on the unit, the Tg of the resinand the desired degree of drying.

A mixture of the polymer dispersion, preferably having a solids contentof 20 to 60%, and the emulsion or, if appropriate, dispersion of thesilicon compound, preferably having a solids content of 20 to 50%, ifappropriate after addition of further auxiliaries, can be sprayed anddried together in the spray drying. Particles which comprise thewater-insoluble organopolymer particles and the particles of the siliconcompound in a matrix of water-soluble protective colloid are obtainedhere.

As an alternative to this procedure, the aqueous organopolymerdispersion and the aqueous emulsion or, if appropriate, dispersion ofthe silicon compound can be sprayed through separate nozzles and driedtogether in the spray tower, if appropriate after addition of furtherauxiliaries. With this procedure, the organopolymer particles and theparticles of the silicon compounds are usually present as separateparticles.

The dispersion powder composition can be employed in the typical fieldsof use. For example, in chemical building products in combination withinorganic, hydraulically setting binders, such as cements (Portland,aluminate, trass, Hüllen, magnesia or phosphate cement), gypsum orwater-glass, for the preparation of building adhesives, plasters,stopper compositions, flooring stopper compositions, joint mortars andpaints. Furthermore as sole binders for coating compositions andadhesives or as binders for textiles. The dispersion powder compositionis preferably employed as a hydrophobizing binder in fields of usewhere, in addition to good adhesion, a reduced uptake of water and/or awater-repellent effect is desired.

EXAMPLES

Preparation of the dispersion powder compositions:

The atomization in Examples 1 to 4 and in the Comparison Example wascarried out in a Nubilosa spray drier:

intake temperature: 100-130° C.

discharge temperature: 65-90° C.

compressed air pressure before

the two-component nozzle: 4 bar

solids content of the dispersions: about 33%

Example 1

A mixture was prepared from a vinyl acetate/ethylene copolymerdispersion (LL 485 from Wacker-Chemie GmbH, solids content about 50%),an aqueous emulsion of isooctyltriethoxysilane (content about 35%), theamount of silane being 2.5% by weight, based on the copolymer, and 8.5%by weight, based on the total amount of copolymer and silane, of aprotective colloid (polyvinyl alcohol W 25/140 from Wacker-Chemie GmbH).This mixture was dried using the above operating data. 10% by weight,based on the total weight of polymeric constituents, of a commerciallyavailable antiblocking agent (mixture of Ca/MgCO₃ and Mg hydrosilicate)was added to the powder thus obtained.

Example 2

The procedure was analogous to Example 1, with the difference that themixture comprised 4.1% by weight of isooctyltriethoxysilane. The powderthus obtained was very readily free-flowing and redispersible.

Example 3

A mixture was prepared analogously to Example 1 from a styrene/butylacrylate copolymer dispersion (LL 476 from Wacker-Chemie GmbH) anaqueous emulsion of isooctyltriethoxysilane, the amount of silane being2.1% by weight, based on the copolymer, and 8.3% by weight, based on thetotal amount of copolymer and silane, of a protective colloid (polyvinylalcohol W 25/140 from Wacker-Chemie GmbH). This mixture was dried usingthe above operating data. 10% by weight, based on the total weight ofpolymeric constituents, of a commercially available antiblocking agent(mixture of Ca/MgCO₃ and Mg hydrosilicate) was added to the powder thusobtained.

Example 4

The procedure was analogous to Example 3, with the difference that themixture comprised 4.2% by weight of isooctyltriethoxysilane. The powderthus obtained was very readily free-flowing and redispersible.

Comparison Example 1

The procedure was analogous to Example 1, with the difference that nosilane was added to the mixture.

Use test:

The products prepared in Examples 1 to 4 and in comparison Example 1were employed in the following joint filler and complete thermalinsulation recipe:

Joint filler recipe:

300.0 parts of Portland cement PZ 35 F

40.0 parts of aluminate cement (HAC-Fondu Lafarge)

649.5 parts of quartz sand (0.1-0.4 mm)

0.5 part of Culminal C 8556

10.0 parts of dispersion powder

200 ml of water per 1000 g of dry mixture

Complete thermal insulation recipe (building adhesive):

280.0 parts of Dykerhoff white cement

500.0 parts of quartz sand (0.1-0.4 mm)

190.0 parts of Jura beads MHS

1.5 parts of Tylose BA 2741

20.0 parts of dispersion powder

20.0 parts of water

Testing of the joint filler recipe:

The flexural tensile strength and compressive strength of cementcompositions prepared with these recipes were tested in accordance withDIN 1164.

The water uptake coefficient was determined in accordance with DIN52617.

The specimens were stored in a standard climate (23° C./50% relativeatmospheric humidity) for 14 days.

The processability was evaluated qualitatively.

The results of testing are summarized in Table 1.

Testing of the building adhesive recipe:

The adhesive strength was determined with a peel-off rate of 250N/safter storage in the dry state for 14 days.

For the water drop test, 0.5 ml of water was applied with a pipette tothe surface of the adhesive composition applied to Styropor and the timetaken for the drop to be absorbed was measured.

The results of testing are summarized in Table 2.

The test results of Table 1 and Table 2 show that the dispersion powdercompositions according to the invention have a hydrophobizing actionwithout adversely changing the mechanical properties here. In contrastto hydrophobizing agents, such as stearates or oleates, which are addedsubsequently to powder mixtures, wetting of the dry mortar with water isnot delayed, but takes place immediately.

TABLE 1 (Testing of the joint filler recipe) Comp. Example 1 2 3 4 Ex. 1Water uptake 0.25 0.20 0.32 0.13 0.76 (kg/m² × h^(0.5)) Flexural 4.6 ±0.4 4.5 ± 0.2 5.7 ± 0.2 5.1 ± 0.4 4.9 ± 0.3 tensile strength (N/mm²)Compressive 16.9 ± 0.4 16.0 ± 0.3 18.0 ± 0.4 18.3 ± 0.5 17.4 ± 0.5strength (N/mm²) Process- somewhat somewhat very very somewhat abilitytacky tacky good good tacky

TABLE 2 (Testing of the adhesive recipe on polystyrene sheets) Comp.Example 1 2 4 Ex. 1 Adhesive 0.1 0.11 0.1 0.11 strength 100% 100% 100%70% (N/mm²) Styropor Styropor Styropor Styropor torn out torn out tornout torn out Water drop 135 min 360 min 360 min 5 min test

What is claimed is:
 1. A process for the preparation of a dispersionpowder composition which is redispersible in water and is based on atleast one water-insoluble film-forming organopolymer, said organopolymerbeing selected from the group consisting of: (a) vinyl ester homo- orcopolymers containing at least one monomer unit selected from the groupconsisting of vinyl esters of unbranched or branched alkylcarboxylicacids having 1 to 15 C atoms; (b) (meth)acrylic acid ester homo- orcopolymers containing at least one monomer unit selected from the groupconsisting of methacrylic acid esters and acrylic acid esters ofalcohols having 1 to 10 C atoms; (c) homo- or copolymers of fumaricand/or maleic acid mono- or diesters of unbranched or branched alcoholshaving 1 to 12 C atoms; (d) homo- or copolymers of dienes, and ofolefins; (e) homo- or copolymers of vinyl aromatics; and (f) homo- orcopolymers of vinyl-halogen compounds; wherein the powder compositioncomprises 0.1 to 30% by weight, based on the organopolymer content, ofat least one water-dispersible silicon compound having a boiling pointunder normal pressure of >160° C. and selected from the group consistingof carbosilanes, carbosiloxanes, tetraorganosilanes, silicic acid estersSi(OR′)₄, organoorganoxysilanes, SiR_(n)(OR′)_(4−n) where n=1 to 3,polysilanes of the formula R₃Si(SiR₂)_(n)SiR₃, where n=0 to 8 andoligosiloxanes of the formula R₃SiO(SiR₂O)_(n)SiR₃, where n=0 to 4 inwhich R′ represents identical or different alkyl radicals oralkoxyalkylene radicals having 1 to 4 C atoms, and R is identical ordifferent, substituted or unsubstituted and denotes branched orunbranched alkyl radicals having 1 to 22 C atoms, cycloalkyl radicalshaving 3 to 10 C atoms, aryl, aralkyl or alkylaryl radicals having 6 to18 C atoms, or halogens, ether, thio-ether, ester, amide, nitrile,hydroxyl, amine, carboxyl, sulfonic acid, carboxylic acid anhydride andcarbonyl groups, and in which, in the case of the polysilanes andoligosiloxanes, R can also have the meaning OR′, said process consistingof spray drying (1) a dispersion of the organopolymer and optionallyauxiliary compounds and (2) an emulsion or dispersion of the siliconcompound and optionally, auxiliary compounds, through separate nozzlesand drying together in a spay tower.
 2. A process for the preparation ofa dispersion powder composition which is redispersible in water and isbased on at least one water-insoluble film-forming organopolymer, saidorganopolymer being selected from the group consisting of: (a) vinylester homo- or copolymers containing at least one monomer unit selectedfrom the group consisting of vinyl esters of unbranched or branchedalkylcarboxylic acids having 1 to 15 C atoms; (b) (meth)acrylic acidester homo- or copolymers containing at least one monomer unit selectedfrom the group consisting of methacrylic acid esters and acrylic acidesters of alcohols having 1 to 10 C atoms; (c) homo- or copolymers offumaric and/or maleic acid mono- or diesters of unbranched or branchedalcohols having 1 to 12 C atoms; (d) homo- or copolymers of dienes, andof olefins; (e) homo- or copolymers of vinyl aromatics; and (f) homo- orcopolymers of vinyl-halogen compounds; wherein the powder compositioncomprises 0.1 to 30% by weight, based on the organopolymer content, ofat least one water-dispersible silicon compound having a boiling pointunder normal pressure of >160° C. and selected from the group consistingof carbosilanes, carbosiloxanes, tetraorganosilanes, silicic acid estersSi(OR′)₄, organoorganoxysilanes, SiR_(n)(OR′)_(4−n) where n=1 to 3,polysilanes of the formula R₃Si(SiR₂)_(n)SiR₃, where n=0 to 8 andoligosiloxanes of the formula R₃SiO(SiR₂O)_(n)SiR₃, where n=0 to 4 inwhich R′ represents identical or different alkyl radicals oralkoxyalkylene radicals having 1 to 4 C atoms, and R is identical ordifferent, substituted or unsubstituted and denotes branched orunbranched alkyl radicals having 1 to 22 C atoms, cycloalkyl radicalshaving 3 to 10 C atoms, aryl, aralkyl or alkylaryl radicals having 6 to18 C atoms, or halogens, ether, thio-ether, ester, amide, nitrile,hydroxyl, amine, carboxyl, sulfonic acid, carboxylic acid anhydride andcarbonyl groups, and in which, in the case of the polysilanes andoligosiloxanes, R can also have the meaning OR′, said process consistingof spraying and drying together, a mixture of a dispersion of theorganopolymer, an emulsion or dispersion of the silicon compound and,optionally, auxiliary compounds.